Binder composition comprising a mixture of a furan resin and an aromatic hydrocarbon-aldehyde condensate



United States Patent BINDER COMPOSITION COMPRISING A MIXTURE OF A FURANRESIN AND AN ARGMATEIC HY- DROCARBON-ALDEHYDE CONDENSA'IE Guido MaxRudolf Lorentz, Oes, Post ()flice Espa, near Butzbach, and WaiterFiilier, Frankfurt am Main, Germany, assignors to Farbwerke HoechstAktiengeselischaft vormals Meister Lucius 8: Bruning, Frankfurt am Main,Germany, a corporation of Germany N0 Drawing. Filed Sept. 26, 1966, Ser.No. 581,682

10 Claims. (Cl. 260-823) ABSTRACT OF THE DISCLOSURE A furan condensationresin derived from precursors such as furfuryl alcohol, furfural, furylacrolein, an aldehyde and combinations thereof, together with acondensation product of a mono-nuclear hydrocarbon such as toluene orxylene with formaldehyde, or a binuclear aromatic hydrocarbon such asnaphthalene with formaldehyde are reacted to produce a hardenablecomposition. Shaped bodies made from this composition containing fillerssuch as coke powder, quartz, sand, etc., show improved non-shrinkbehavior. As an optional additive for the aromatic hydrocarbon, a phenolmay be used of which 4,4-dihydroxy-Z,2-diphenylpropane is a preferredillustration.

The present application is a continuation-in-part of application Ser.No. 285,215 filed June 4, 1963, now abancloned.

The present invention relates to a hardenable synthetic resincomposition to be used as binder for the manufacture of acid-proofmaterials for constructions. The present invention particularly relatesto a binder for acidproof and chemically resistant cements which binderdoes not shrink during hardening.

In the first place, hardenable furan resins and hardenable phenolresins, so-called resols, are used as binders for acid-proofconstruction materials. When being used, the aforesaid resins are mixedwith a filler, for example quartz sand, graphite powder, coke powder,asbestos, rutile, barium sulfate, and an acid hardener, whereupon theyharden to a solid, pressure-resistant body having a high resistance tothe action of chemical substances. Suitable hardeners are acid compoundssuch as mineral acids, especially however p-toluene-sulfonic acid,p-toluene-sulfochloride, naphthalene-disulfonic acid, p-toluene-sulfonicacid ethyl ester and the like.

The furan resins have the disadvantage that they shrink duringhardening, that is to say their volume decreases whereby tensions occurin the construction built therewith. Moreover, they have a littleresistance to alkalies.

Phenol resins often cause skin irritations with persons handling them.

It is known to harden furan resins together with phenol resins. In thiscase, the resistance to chemicals of the hardened resin compositions isconsiderably better than that of the individual components. Theshrinkage of the furan resins cannot be avoided, however, by the joinedprocessing with phenol resins. Moreover, the mixtures still have theskin irritating properties of the phenol resins contained therein.

Now, we have found hardenable synthetic resin compositions suitable asbinders for acid-proof building materials, which compositions do notshrink during hardening and do not cause any irritation of the skin.

The hardenable synthetic resin compositions according to the inventioncontain as component A 90 to 60 parts by weight of a furan resin and ascomponent B 10 to parts by weight of a condensation product obtainedfrom an aromatic, monoor binuclear hydrocarbon and formaldehyde in thepresence of a strong acid and having an oxygen content of at least 5%and a sulfur content of less than 0.3%.

It is surprising that synthetic resin compositions of the aforesaid typecan be hardened in the cold under the action of acid catalysts and withco-condensation, although condensation products of aromatic hydrocarbonsand formaldehyde alone are not liable to acid hardening.

Furan resins are resinous products obtained by condensation of furfurylalcohol, furfural or of furfural with aldehydes, especiallyacetaldehyde. The manufacture of condensation resins from furfurylalcohol in the presence of sulfuric acid is described, for example, inHouben-Weyl, 4th ed. 1963, vol. XIV/2, p. 636, Georg Thieme Verlag,Stuttgart.

Reference is also made to US. Patent 2,471,600 where the manufacture ofresins of this type is likewise described. Further references to themanufacture and hardening of furan resins are to be found inDunlop-Peters The Furans, p. 220 to 224 and 783 et seq., ReinholdPublishing Corporation, New York. The manufacture of furyl acroleinresins is described in US. Patent 3,063,959, p. l, first column, lines50 et seq.

The manufacture of condensation resins from aromatic hydrocarbons andformaldehyde is disclosed in Houben- Weyl, 4th ed, vol. XIV/2, p. 313 etseq. Formaldehyde is condensed with the aromatic hydrocarbon at about100 C. in the presence of a strong acid, advantageously sulfuric acid.

To prepare the compositions according to the invention resins obtainedby condensation of formaldehyde with toluene, xylene, mesitylene ornaphthalene are especially suitable. These resins may be modified withphenols. Up to 30 parts by weight of a phenol may be added to 100 partsof the aromatic hydrocarbon. Especially valuable products are obtainedwhen modifying with 4,4'-dihydroxy-2,2-diphenylpropane (Bisphenol A).Other phenols, for example phenol, o-cresol, or4,4'-dihydroxy-diphenylmethane may also be used.

The hardenable compositions according to the invention are obtained bymixing the furan resin with the resin from formaldehyde and aromatichydrocarbon and homogenizing the mixture obtained, for example withstirring, shaking or a similar procedure. Sometimes, it is advantageousto add to the furan resin the resin from the aromatic hydrocarbon andformaldehyde in the form of a solution in an aromatic hydrocarbon,preferably benzene, toluene or xylene. After mixing the components, thesolvent can be eliminated by distillation.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the parts being by Weight unlessotherwise stated.

Example 1 70 parts of furan resin obtained by condensation of furfurylalcohol in the presence of sulfuric acid and 30 parts of a 40% solutionof a condensation product from toluene and formaldehyde in toluene weremixed and the solvent was distilled off. 100 parts of the mixtureobtained contained parts of furan resin and 15 parts of the resin fromaromatic hydrocarbon and formaldehyde. The resin from toluene andformaldehyde contained 16% of oxygen and less than 0.3% of sulfur.

60 parts of the resin composition were mixed with parts of a fillerconsisting of 96 parts of coke powder having a particle size of up to0.4 millimeter and 4 parts of p-toluene-sulfonic acid. The cementobtained had a working time of 30 minutes and a hardening time of 24hours (to a Shore hardness D of about 40). A shaped body made from thecement shrunk slightly during the first 3 10 days but after 15 days ithad recovered its original length.

Example 2 70 parts of the furan resin described in Example 1 were mixedwith 30 parts of a condensation product from xylene and formaldehydehaving an oxygen content of 11% and a sulfur content of less than 0.3%.A cement was prepared from 100 parts of the resin composition and 375parts of quartz sand having a particle size of up to 1 millimeter andcontaining 3%, calculated on the sand, of naphthalene-disulphonic acid.The properties of the cement were analogous to those of the cement ofExample 1.

Example 3 85 parts of the furan resin of Example 1 were mixed with 15parts of a mixture of 90 parts of a condensation product from axylene-formaldehyde resin and 10 parts of4,4-dihydroxy-2,2-diphenyl-propane (Bisphenol A).

A cement was prepared from 25 parts of the resin mixture obtained and100 parts of a filler consisting of 97 parts of quartz powder and 3parts of p-toluenesulfonic acid. The working time and the hardeningproperties of the cement were analogous to those of the cement ofExamples 1 and 2.

The resin composition could also be hardened in the heat by adding 2parts of p-toluenesulfonic acid ethyl ester instead of 3 parts ofp-toluenesulfonic acid. The hardening commenced at 70 C. When thehardening temperature was raised to 150 C. an acid hardener could bedispensed with.

Example 4 70 parts of a condensation product from furfuryl alcohol werediluted with 30 parts of furfural. 70 parts of the furan resin obtainedwere mixed with 30 parts of a solution of 45% strength of a condensationproduct from xylene and formaldehyde in xylene and the solvent waseliminated. The resin composition obtained contained 83.5 parts of furanresin and 16.5 parts of the condensation product from xylene andformaldehyde having an oxygen content of 11% and a sulfur content ofless than 0.3% i A cement was prepared from 60 parts of the resincomposition obtained and 100 parts of a filler consisting of 96 parts ofcoke powder having a particle size of up to 0.4 millimeter and 4 partsof p-toluenesulfonic acid. The cement had a working time of 30 minutesand a hardening time of 24 hours to a Shore hardness D of about 40.

Example 5 50 parts of a furyl-acrolein resin, obtained by condensationof furfural and acetaldehyde, were mixed with 50 parts of a 45% solutionof a condensation product from xylene and formaldehyde in xylene and thesolvent was distilled off. The resin composition freed from the solventcontained 69 parts of furan resin and 31 parts of the condensationproduct from xylene and formaldehyde. A cement was prepared by mixing100 parts of the aforesaid resin composition with 375 parts of a fillerconsisting of quartz sand having a particle size of up to 1 millimeterand 3% of naphthalene-disulfonic acid as hardener. The properties of thecement were similar to those of the cements of the preceding examples.

Example 6 55 parts of the furan resin specified in Example 4 were mixedwith a 45% solution of a condensation product from mesitylene andformaldehyde in benzene and the solvent was distilled off. The remainingresin composition contained 71.5 parts of the furan resin and 28.5 partsof the condensation product from mesitylene and formaldehyde having anoxygen content of 12.3% and a sulfur content of less than 0.3%. A cementwas prepared from 100 parts of the resin composition and 375 parts ofthe mixture of sand and naphthalene-disulfonic acid used in 4- Example 7Example 5. The properties of the cement obtained corresponded to theproperties of the cements described in the preceding examples.

60 parts of a furan resin consisting of 70 parts of a condensationproduct from furfuryl alcohol and 30 parts of furfural were mixed with40 parts of a condensation product from xylene and formaldehyde havingan oxygen content of 17.3% and a sulfur content of less than 0.3%. partsof the resin composition were mixed with 375 parts of quartz sand havinga particle size of up to 1 millimeter and containing 3% ofnaphthalene-disulfonic acid. The cement obtained had the same workingtime and hardening properties as the cements described above.

Example 8 70 parts of a furyl-acrolein resin obtained by alkalinecondensation of furfural with acetaldehyde were mixed with 30 parts of acondensation product from 70 parts of xylene and 30 parts of o-cresolwith formaldehyde. The condensation product from xylene, cresol andformaldehyde had an oxygen content of 22% and a sulfur content of lessthan 0.3%.

The properties of the resin composition corresponded to the propertiesof the composition of Example 3. Hardening could be brought about eitherin the cold with ptoluenesulfonic acid or in the heat withp-toluenesulfonic acid ethyl ester. When temperatures above C. wereapplied a hardener need not be added.

What is claimed is:

1. A hardenable composition of matter consisting essentially of amixture of:

(A) 90-60% by weight of a furan condensation resin selected from atleast one member of the group consisting of furfuryl alcohol, furfural,furfural with an aldehyde and furyl acrolein and (B) 10-40% by weight ofa condensation product of a monoor binuclear aromatic hydrocarbon withformaldehyde having an oxygen content of at least 5% and a sulfurcontent of less than 0.3%.

2. The composition of claim 1, wherein component B is a condensationproduct of a monoor binuclear aromatic hydrocarbon with formaldehyde, towhich are added 0-30 parts by weight of a phenol.

3. The composition of claim 1, which, in addition, contains a filler.

4. The composition of claim 1, wherein component A is a furfuryl alcoholcondensation product.

5. The composition of claim 1, wherein component A is a condensationproduct of furfuryl alcohol and furfu-ral.

6. The composition of claim 1, wherein component A is a condensationproduct of furfural with acetaldehy'de.

7. The composition of claim 1, wherein component B is a tolueneformaldehyde condensation product.

8. The composition of claim 1, wherein component B is a xyleneformaldehyde condensation product.

9. The composition of claim 1, wherein component B is a mesityleneformaldehyde condensation product.

10. The composition of claim 1, wherein component B is a condensationproduct of 90 parts by weight of xylene and 10 parts by weight of4,4-dihydroxy-2,2-diphenylpropane.

References Cited UNITED STATES PATENTS 3,053,793 9/1962 Imoto et a1260-838 3,057,026 10/ 1962 Blaies et al. 260829 3,063,959 11/ 1962Lorentz 260-838 3,165,558 1/ 1965 Imoto et a1. 260-823 GEORGE F. LESMES,Primary Examiner.

MURRAY TILLMAN, Examiner.

I. C. BLEUTQE, Assistant Examiner.

